CN110201656A - A kind of preparation method of TiO 2-based catalyst carrier - Google Patents
A kind of preparation method of TiO 2-based catalyst carrier Download PDFInfo
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- CN110201656A CN110201656A CN201910494828.XA CN201910494828A CN110201656A CN 110201656 A CN110201656 A CN 110201656A CN 201910494828 A CN201910494828 A CN 201910494828A CN 110201656 A CN110201656 A CN 110201656A
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- tio
- based catalyst
- catalyst carrier
- metatitanic acid
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- 239000003054 catalyst Substances 0.000 title claims abstract description 97
- 229910010413 TiO 2 Inorganic materials 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 97
- 239000002253 acid Substances 0.000 claims abstract description 60
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 56
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 55
- 239000004411 aluminium Substances 0.000 claims abstract description 52
- 239000000843 powder Substances 0.000 claims abstract description 50
- 239000003292 glue Substances 0.000 claims abstract description 45
- 239000007864 aqueous solution Substances 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000000853 adhesive Substances 0.000 claims abstract description 25
- 230000001070 adhesive effect Effects 0.000 claims abstract description 25
- 238000007906 compression Methods 0.000 claims abstract description 23
- 230000006835 compression Effects 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 21
- 239000011148 porous material Substances 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 17
- 230000001404 mediated effect Effects 0.000 claims abstract description 8
- 235000010215 titanium dioxide Nutrition 0.000 claims description 43
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000013067 intermediate product Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 229910001593 boehmite Inorganic materials 0.000 claims description 6
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical group O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 2
- XFBXDGLHUSUNMG-UHFFFAOYSA-N alumane;hydrate Chemical compound O.[AlH3] XFBXDGLHUSUNMG-UHFFFAOYSA-N 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 abstract description 28
- 239000002994 raw material Substances 0.000 abstract description 17
- 210000003850 cellular structure Anatomy 0.000 abstract description 6
- PXFBZOLANLWPMH-UHFFFAOYSA-N 16-Epiaffinine Natural products C1C(C2=CC=CC=C2N2)=C2C(=O)CC2C(=CC)CN(C)C1C2CO PXFBZOLANLWPMH-UHFFFAOYSA-N 0.000 abstract description 5
- 238000000354 decomposition reaction Methods 0.000 abstract description 4
- 239000007767 bonding agent Substances 0.000 abstract description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 17
- 239000005864 Sulphur Substances 0.000 description 17
- 230000000694 effects Effects 0.000 description 11
- 238000000465 moulding Methods 0.000 description 11
- 230000008859 change Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- 229920000609 methyl cellulose Polymers 0.000 description 5
- 239000001923 methylcellulose Substances 0.000 description 5
- 238000007493 shaping process Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- IYVLHQRADFNKAU-UHFFFAOYSA-N oxygen(2-);titanium(4+);hydrate Chemical class O.[O-2].[O-2].[Ti+4] IYVLHQRADFNKAU-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 241000790917 Dioxys <bee> Species 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 125000001741 organic sulfur group Chemical group 0.000 description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- -1 carboxy-propyl Chemical group 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000001038 titanium pigment Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of preparation methods of TiO 2-based catalyst carrier, the detailed process of this method are as follows: the water-soluble bonding agent of aluminium glue and pore creating material are added into metatitanic acid powder, it mediated, squeeze to obtain strip particle, strip particle is successively dried and roasted, TiO 2-based catalyst carrier is obtained.The present invention is using metatitanic acid powder as raw material, adhesive aluminium glue aqueous solution is added and pore creating material prepares TiO 2-based catalyst carrier, in subsequent roasting process, the aluminium glue aqueous solution for being evenly distributed on metatitanic acid powder surface resolves into the aluminium oxide with stronger affine cementitiousness, enhance the active force between the decomposition product titanium dioxide of metatitanic acid powder, to improve the compression strength of TiO 2-based catalyst carrier, cellular structure abundant and biggish carrier specific surface area are still remained simultaneously, TiO 2-based catalyst carrier is set to have both high-specific surface area and high compressive strength.
Description
Technical field
The invention belongs to catalyst technical fields, and in particular to a kind of preparation method of TiO 2-based catalyst carrier.
Background technique
Titanium dioxide (TiO2) be taken seriously as a kind of novel catalyst carrier material is standby.Since titanium dioxide has
Unique property can occur " strong interaction " with the noble metal of load, the absorption of catalyst and catalytic performance is made to change,
Activity has large change with selectivity, at the same make catalyst also and have anti-toxicity is strong, low temperature active is good, surface acidity is adjustable and
The advantages that high temperature reducibility.The Co/Mo organic hydrogenation reforming catalyst active component prepared using titanium dioxide as carrier is negative
Carrying capacity is only using aluminium oxide as 2/3rds of carried catalyst, but activity is carried catalyst much higher than aluminium oxide, especially
Activity is more outstanding at low temperature.Therefore titanium dioxide as catalyst carrier the fields such as chemical industry, petrochemical industry, environmental protection, the energy all
With highly important application value.Although titania support has huge prospects for commercial application, current various aspects
Research is not mature enough, still in the on probation and development phase, titanium deoxide catalyst in the prior art be mostly it is powdered, so
And most industrial productions are it is desirable that using titanium dioxide forming substances as catalyst or carrier, this just needs titanic oxide shaping to carry
Body should have good compression strength and antiwear property, could effectively extend the service life of catalyst.
About TiO2The preparation method domestic and foreign scholars of carrier have carried out some highly beneficial explorations.Existing research is big
It is mostly with TiO2Powder or titanium dioxide hydrates slurry are raw material to prepare shaping carrier.Using commercially available TiO2Powder is raw material
Prepared shaping carrier specific surface area very little, it is necessary to special TiO2Powder is raw material.Such as public affairs in Chinese patent CN1269787
It has opened using pyrogenic titanium dioxide as main component, with 0.1~5% organic acid or inorganic before shaping or after molding
Acid processing is to prepare suitable catalyst, gained molding surface area 37m2/ g, cutting hardness only 25N.Chinese patent
CN1778466, which is disclosed, prepares TiO by raw material of nano titanium dioxide powder2The method of molding, nano titanium dioxide powder
Specific surface area in 200m2/ g or more, prepared TiO230~150N/cm of side pressure strength of molding, specific surface area 5~
170m2/g.Often cost of material is higher for this method.
The TiO prepared using titanium dioxide hydrates slurry as raw material2Molding also studies have reported that, due to TiO2 hydrate
Solid holdup is low, is unable to straight forming, to be generally first dried to be formed after powder adds suitable adjuvants modulation.Chinese patent
The intermediate wet metatitanic acid that CN1348834A uses sulfuric acid method titanium pigment to produce is primary raw material, through 110 DEG C of crushed after being dried
Be made metatitanic acid dry powder, pore creating material be added, the circular granular of diameter 5mm is kneaded, squeezed, is shaped to adhesive, through drying,
It is heat-treated and TiO is made2Based catalyst carrier, the surface area of carrier is up to 4~20m2/ g, compression strength 80~150N/.The U.S.
Patent CN1149261A is greater than 200m with dry specific surface area2The titanium dioxide hydrates slurry of/g is as raw material, through drying
Peptizing agent HNO is added up to after 15~40% in burn tinctuer3Or formic acid and organic binder starch, the diameter 3.5mm of preparation, length
The strip molding of 1.5~15mm is spent after 350 DEG C of roastings, and surface area is up to 178m2/ g, but crushing strength only 16N, if will
Maturing temperature is increased to 950 DEG C, and 191.7N can be improved in crushing strength, but surface area drops to 2.5m2/g.Peace will is strong etc. to be had studied
Nanometer titanium dioxide titanium valve is added in metatitanic acid and prepares TiO2The method of molding, studies have shown that nano-titanium dioxide used
Powder diameter is smaller, prepared TiO2Molding intensity is higher, specific surface area is bigger；The ratio that metatitanic acid accounts for is big, although made
Standby TiO2Molding large specific surface area, but intensity difference.It is mentioned in WO2006048424 patent, titanium dioxide hydrates slurry warp
120 DEG C are dried to obtain TiO of the raw material powder than wet cake straight forming2Molding intensity substantially reduces.Although using titanium dioxide
The TiO of hydrate slurry preparation2Molding cost of material is low, due to TiO2Hydrate solid holdup is low, the energy consumption in drying process
Height, low efficiency, and drying means can generate large effect to the performance of shaping carrier.
Summary of the invention
Technical problem to be solved by the present invention lies in view of the above shortcomings of the prior art, provide a kind of titanium dioxide
The preparation method of based catalyst carrier.Adhesive aluminium glue aqueous solution and pore creating material is added using metatitanic acid powder as raw material in this method
TiO 2-based catalyst carrier is prepared, in subsequent roasting process, the aluminium glue aqueous solution for being evenly distributed on raw material surface is decomposed
At the aluminium oxide with stronger affine cementitiousness, the active force between the decomposition product titanium dioxide of metatitanic acid is enhanced, from
And the compression strength of TiO 2-based catalyst carrier is improved, while still remaining cellular structure abundant and biggish load
Surface area per unit volume product, makes TiO 2-based catalyst carrier have both high-specific surface area and high compressive strength.
In order to solve the above technical problems, the technical solution adopted by the present invention is that: a kind of TiO 2-based catalyst carrier
Preparation method, which is characterized in that the detailed process of this method are as follows: adhesive and pore creating material are added into metatitanic acid powder, through pinching
Conjunction, extruding obtain strip particle, and strip particle is successively dried and roasted, TiO 2-based catalyst carrier is obtained；Institute
Stating adhesive is aluminium glue aqueous solution, the preparation process of the aluminium glue aqueous solution are as follows: hydrated alumina is added to mass concentration
For Aluminum sol is made in 30% aqueous solution of nitric acid, then plus water is deployed to obtain the aluminium glue that alumina content is 40g/L~50g/L
Aqueous solution；The additional amount of the aluminium glue aqueous solution is the 35%~45% of metatitanic acid powder quality；The additional amount of the pore creating material
It is the 3%~5% of metatitanic acid powder quality.
In the prior art using the carrier of metatitanic acid powder preparation, compression strength and specific surface area are difficult to take into account.This hair
It is bright using metatitanic acid powder as raw material, the water-soluble bonding agent of aluminium glue is added and TiO 2-based catalyst load is prepared in pore creating material
After body, aluminium glue aqueous solution and metatitanic acid powder immixture, it is evenly distributed on the surface of metatitanic acid powder particle, it is subsequent to roast
Cheng Zhong, the metatitanic acid in strip particle are decomposed into titanium dioxide, and pore creating material resolves into gas and forms porous knot in titanium dioxide
Structure, aluminium glue aqueous solution resolve into aluminium oxide, since aluminium oxide has stronger affine cementitiousness, enhance between metatitanic acid particle
Active force, that is, the active force between titanium dioxide is enhanced, to improve the compression strength of TiO 2-based catalyst carrier；
In addition, in subsequent drying and roasting technique, the original cellular structure abundant of metatitanic acid and biggish carrier specific surface
Product is largely retained, and ensure that the load performance of TiO 2-based catalyst carrier.
A kind of preparation method of above-mentioned TiO 2-based catalyst carrier, which is characterized in that the metatitanic acid powder by
It is prepared using the intermediate product metatitanic acid of Titanium White Production By Sulfuric Acid Process through drying, crushing, the ratio table of the metatitanic acid powder
Area is 150m2/ g~200m2/g.The metatitanic acid powder in above-mentioned source is cheap and easy to get, reduces TiO 2-based catalyst carrier
Cost of material, and the metatitanic acid powder in above-mentioned source have cellular structure abundant, specific surface area is higher, is fired into two
Titanium oxide can retain its cellular structure.
The preparation method of above-mentioned a kind of TiO 2-based catalyst carrier, which is characterized in that the pore creating material is carboxylic first
Base cellulose or hydroxypropyl cellulose.Above-mentioned pore creating material is from a wealth of sources, is easy to get, and reduces TiO 2-based catalyst carrier
Preparation difficulty.
A kind of preparation method of above-mentioned TiO 2-based catalyst carrier, which is characterized in that the hydrated alumina
For boehmite or aluminium hydroxide.The hydrated alumina of mentioned kind is common hydrated alumina in industry, roasting
Activated alumina is produced afterwards, and cheap, further reduced the preparation cost of TiO 2-based catalyst carrier.
A kind of preparation method of above-mentioned TiO 2-based catalyst carrier, which is characterized in that the process of the drying are as follows:
First in 60 DEG C~80 DEG C dry 2h~3h, then in 110 DEG C~120 DEG C dry 3h~5h.Using the drying mode convenient for control
Dry rate-of-loss of coolant prevents the dehydration of strip particle surface too fast, gives birth in stress and generate section inside it, leads to dioxy
Change the compression strength decline of titanium-based catalyst carrier.
The preparation method of above-mentioned a kind of TiO 2-based catalyst carrier, which is characterized in that the temperature of the roasting is
350 DEG C~500 DEG C, the time is 2h~4h.Under the roasting technique parameter, the metatitanic acid in bar shaped particle is resolved into after drying
The titanium dioxide of anatase titanium dioxide, while ensure that and resolve into gas by pore creating material to form porous structure, aluminium glue in titanium dioxide water-soluble
Liquid resolves into going on smoothly for aluminium oxide, avoids the excessively high titanium dioxide for leading to anatase titanium dioxide of maturing temperature and mutually becomes low specific surface
The long-pending red stone titanium dioxide of crystalline substance, to reduce the specific surface area of TiO 2-based catalyst carrier.
The preparation method of above-mentioned a kind of TiO 2-based catalyst carrier, which is characterized in that described titania-based to urge
The specific surface area of agent carrier is 100m2/ g~160m2/ g, compression strength are 100N/cm~120N/cm.The present invention is prepared
TiO 2-based catalyst carrier taken into account specific surface area and compression strength, and it is raw materials used be easily obtained, it is cheap, together
When preparation process it is simple, be easy to industrial production.
Compared with the prior art, the present invention has the following advantages:
1, the present invention uses metatitanic acid powder for raw material, and adhesive aluminium glue aqueous solution is added and pore creating material prepares titanium dioxide
Based catalyst carrier, in subsequent roasting process, the aluminium glue aqueous solution for being evenly distributed on raw material surface resolves into aluminium oxide, due to
Aluminium oxide has stronger affine cementitiousness, the active force between the decomposition product titanium dioxide of metatitanic acid is enhanced, to mention
The high compression strength of TiO 2-based catalyst carrier, while still remaining cellular structure abundant and biggish carrier ratio
Surface area makes TiO 2-based catalyst carrier have both high-specific surface area and high compressive strength.
2, the specific surface area for the TiO 2-based catalyst carrier that the present invention is prepared is 100m2/ g~160m2/ g resists
Compressive Strength is 100N/cm~120N/cm, can satisfy industrial application requirement completely, has fine prospects for commercial application.
3, of the invention to prepare that raw material metatitanic acid powder is cheap to be easy to get, the water-soluble bonding agent of aluminium glue and pore creating material it is simple easily
, preparation cost is greatly reduced, and preparation process is simple, is suitable for large-scale industrial production.
4, TiO 2-based catalyst carrier of the invention specific surface area with higher (connects with conventional oxidation alumina supporter
Closely), the titanium elements and in carrier have facilitation to the activity of molybdenum system Organic sulphur hydrogenation catalyst, so that reducing molybdenum system has
The dosage of machine sulphur hydrogenation catalyst, improves the activity of molybdenum system Organic sulphur hydrogenation catalyst, therefore of the invention titania-based
Catalyst carrier is properly applied to Organic sulphur hydrogenation catalyst.
Technical solution of the present invention is described in further detail below by embodiment.
Specific embodiment
The preparation process of adhesive aluminium glue aqueous solution in 1~embodiment of the embodiment of the present invention 7 are as follows: by hydrated alumina
It being added in the aqueous solution of nitric acid that 100mL mass concentration is 30% and Aluminum sol is made, the water that 700mL is then added stirs evenly,
Obtain the aluminium glue aqueous solution that alumina content is 40g/L~50g/L.
Embodiment 1
The detailed process of the present embodiment are as follows: 38g adhesive aluminium glue aqueous solution and 3g carboxylic are added into 100g metatitanic acid powder
Methylcellulose is mediated, squeezes to obtain the strip particle that diameter is 4mm, which is put into valve bag and is sealed, first
It in 60 DEG C of dry 3h, then takes out in 110 DEG C of dry 4h, then in 350 DEG C of roasting 5h, obtains granular titania-based catalysis
Agent carrier；The metatitanic acid powder by using Titanium White Production By Sulfuric Acid Process intermediate product metatitanic acid through drying, crush preparation and
, the specific surface area of the metatitanic acid powder is 163m2/g；The specific surface area of the TiO 2-based catalyst carrier is
145m2/ g, compression strength 117N/cm.
The hydrated alumina that the present embodiment prepares adhesive aluminium glue aqueous solution is boehmite, oxygen in aluminium glue aqueous solution
Change aluminium content is 45g/L.
Comparative example 1
This comparative example difference from example 1 is that: be added without pore creating material carboxymethyl cellulose；The titanium dioxide
The specific surface area of based catalyst carrier is 72m2/ g, compression strength 126N/cm.
By comparative example 1 compared with embodiment 1 it is found that in embodiment 1 be added pore creating material carboxymethyl cellulose, can be in titanium dioxide
Titanium-based catalyst carrier forms porous structure, substantially increases the specific surface area of TiO 2-based catalyst carrier, simultaneously because
The compression strength of the generation of porous structure, TiO 2-based catalyst carrier slightly decreases.
Comparative example 2
This comparative example difference from example 1 is that: be added without homemade adhesive aluminium glue aqueous solution；The dioxy
The specific surface area for changing titanium-based catalyst carrier is 87m2/ g, compression strength 22N/cm.
By comparative example 2 it is found that adhesive aluminium glue aqueous solution is added in embodiment 1 compared with embodiment 1, in roasting process,
Aluminium glue aqueous solution decomposes the aluminium oxide for generating and having preferable affine adhesive force, enhances the decomposition product titanium dioxide of metatitanic acid
Between active force, to improve the compression strength of TiO 2-based catalyst carrier, while still remaining former duct abundant
Structure and biggish carrier specific surface area, make TiO 2-based catalyst carrier have both high-specific surface area and high compressive strength.
Embodiment 2
The detailed process of the present embodiment are as follows: 35g adhesive aluminium glue aqueous solution and 3g carboxylic are added into 100g metatitanic acid powder
Methylcellulose is mediated, squeezes to obtain the strip particle that diameter is 4mm, which is put into valve bag and is sealed, first
It in 60 DEG C of dry 2h, then takes out in 115 DEG C of dry 5h, then in 500 DEG C of roasting 2h, obtains granular titania-based catalysis
Agent carrier；The metatitanic acid powder by using Titanium White Production By Sulfuric Acid Process intermediate product metatitanic acid through drying, crush preparation and
, the specific surface area of the metatitanic acid powder is 199m2/g；The specific surface area of the TiO 2-based catalyst carrier is
134m2/ g, compression strength 112N/cm.
The hydrated alumina that the present embodiment prepares adhesive aluminium glue aqueous solution is boehmite, oxygen in aluminium glue aqueous solution
Change aluminium content is 42g/L.
Embodiment 3
The detailed process of this method of the present embodiment are as follows: it is water-soluble that 45g adhesive aluminium glue is added into 100g metatitanic acid powder
Liquid and 4g carboxymethyl cellulose are mediated, squeeze to obtain the strip particle that diameter is 4mm, which is put into valve bag
Middle sealing then takes out in 115 DEG C of dry 4h, then in 350 DEG C of roasting 4h, obtain granular dioxy first in 75 DEG C of dry 3h
Change titanium-based catalyst carrier；The metatitanic acid powder by using Titanium White Production By Sulfuric Acid Process intermediate product metatitanic acid through drying,
Crushing is prepared, and the specific surface area of the metatitanic acid powder is 199m2/g；The ratio table of the TiO 2-based catalyst carrier
Area is 158m2/ g, compression strength 103N/cm.
The hydrated alumina that the present embodiment prepares adhesive aluminium glue aqueous solution is boehmite, oxygen in aluminium glue aqueous solution
Change aluminium content is 40g/L.
Embodiment 4
The detailed process of the present embodiment are as follows: 40g adhesive aluminium glue aqueous solution and 4g carboxylic are added into 100g metatitanic acid powder
Methylcellulose is mediated, squeezes to obtain the strip particle that diameter is 4mm, which is put into valve bag and is sealed, first
It in 70 DEG C of dry 2.5h, then takes out in 120 DEG C of dry 3h, then in 410 DEG C of roasting 3h, obtains granular titania-based urge
Agent carrier；The metatitanic acid powder is prepared by the intermediate product metatitanic acid using Titanium White Production By Sulfuric Acid Process through drying, crushing
And obtain, the specific surface area of the metatitanic acid powder is 187m2/g；The specific surface area of the TiO 2-based catalyst carrier is
129m2/ g, compression strength 110N/cm.
The hydrated alumina that the present embodiment prepares adhesive aluminium glue aqueous solution is boehmite, oxygen in aluminium glue aqueous solution
Change aluminium content is 50g/L.
Embodiment 5
The detailed process of the present embodiment are as follows: 45g adhesive aluminium glue aqueous solution and 5g carboxylic are added into 100g metatitanic acid powder
Methylcellulose is mediated, squeezes to obtain the strip particle that diameter is 4mm, which is put into valve bag and is sealed, first
It in 80 DEG C of dry 2h, then takes out in 120 DEG C of dry 3h, then in 490 DEG C of roasting 3h, obtains granular titania-based catalysis
Agent carrier；The metatitanic acid powder by using Titanium White Production By Sulfuric Acid Process intermediate product metatitanic acid through drying, crush preparation and
, the specific surface area of the metatitanic acid powder is 152m2/g；The specific surface area of the TiO 2-based catalyst carrier is
106m2/ g, compression strength 102N/cm.
The hydrated alumina that the present embodiment prepares adhesive aluminium glue aqueous solution is aluminium hydroxide, is aoxidized in aluminium glue aqueous solution
Aluminium content is 40g/L.
Embodiment 6
The present embodiment difference from example 1 is that: the pore creating material be carboxy-propyl cellulose；The titanium dioxide
The specific surface area of based catalyst carrier is 159m2/ g, compression strength 115N/cm.
The hydrated alumina that the present embodiment prepares adhesive aluminium glue aqueous solution is aluminium hydroxide, is aoxidized in aluminium glue aqueous solution
Aluminium content is 46g/L.
Embodiment 7
The detailed process of the present embodiment are as follows: 39g adhesive aluminium glue aqueous solution and 3g carboxylic are added into 100g metatitanic acid powder
Methylcellulose is mediated, squeezes to obtain the strip particle that diameter is 4mm, which is put into valve bag and is sealed, first
It in 80 DEG C of dry 3h, then takes out in 115 DEG C of dry 3h, then in 350 DEG C of roasting 5h, obtains granular titania-based catalysis
Agent carrier；The metatitanic acid powder by using Titanium White Production By Sulfuric Acid Process intermediate product metatitanic acid through drying, crush preparation and
, the specific surface area of the metatitanic acid powder is 152m2/g；The specific surface area of the TiO 2-based catalyst carrier is
106m2/ g, compression strength 102N/cm.
The hydrated alumina that the present embodiment prepares adhesive aluminium glue aqueous solution is aluminium hydroxide, is aoxidized in aluminium glue aqueous solution
Aluminium content is 50g/L.
By the TiO 2-based catalyst carrier prepared in the embodiment of the present invention 1 and commercially available alumina support (specific surface
Product is 173m2/ g, compression strength 106N/cm) load C o, Mo Organic sulphur hydrogenation catalyst, detailed process is made are as follows: by seven
Ammonium molybdate is dissolved in the ammonium hydroxide that volume fraction is 15%, and a small amount of ethylenediamine is then added, adds cobalt nitrate, is heated to 60 DEG C of stirrings
It is clarified to solution, is impregnated, dried using the TiO 2-based catalyst carrier of equivalent or alumina support as raw material, then
2h is roasted at 450 DEG C, obtains titanium dioxide base carrier Organic sulphur hydrogenation catalyst and alumina support Organic sulphur hydrogenation catalyst；
The physical index of titanium dioxide base carrier Organic sulphur hydrogenation catalyst and alumina support Organic sulphur hydrogenation catalyst is examined
Assessment valence, and professional standard HG2514-2006 " Organic sulphur hydrogenation catalyst activity test method " is used, using two kinds of different loads
The Organic sulphur hydrogenation catalyst of body carries out Organic sulfur hydro-conversion reaction experiment, carries out detection evaluation to the catalytic performance of the two,
As a result as shown in table 1 below.
The physics of 1 titanium dioxide base carrier Organic sulphur hydrogenation catalyst of table and alumina support Organic sulphur hydrogenation catalyst refers to
Mark and catalytic performance
As known from Table 1, the titanium dioxide base carrier organic sulfur prepared using the titanium dioxide base carrier of the embodiment of the present invention 1
Hydrogenation catalyst is to the load capacity of catalyst activity component molybdenum trioxide and cobalt compared with alumina support Organic sulphur hydrogenation catalyst
About 1/3 is reduced to the load capacity of catalyst activity component molybdenum trioxide and cobalt, titanium dioxide base carrier Organic sulphur hydrogenation catalyst
Specific surface area it is small compared with the specific surface area of alumina support Organic sulphur hydrogenation catalyst, but titanium dioxide base carrier organic sulfur adds hydrogen
The catalytic activity of catalyst is improved compared with alumina support Organic sulphur hydrogenation catalyst illustrates method of the invention not only by about one time
The load capacity of catalyst activity component is saved, while substantially increasing the activity of catalyst.
The above is only presently preferred embodiments of the present invention, is not intended to limit the invention in any way.It is all according to invention skill
Art any simple modification, change and equivalence change substantially to the above embodiments, still fall within technical solution of the present invention
Protection scope in.
Claims (7)
1. a kind of preparation method of TiO 2-based catalyst carrier, which is characterized in that the detailed process of this method are as follows: to inclined titanium
Adhesive and pore creating material are added in sour powder, mediated, squeeze to obtain strip particle, strip particle is successively dried and roasted
It burns, obtains TiO 2-based catalyst carrier；Described adhesive is aluminium glue aqueous solution, the preparation process of the aluminium glue aqueous solution
Are as follows: hydrated alumina is added in the aqueous solution of nitric acid that mass concentration is 30%, Aluminum sol is made, then plus water is deployed
The aluminium glue aqueous solution for being 40g/L~50g/L to alumina content；The additional amount of the aluminium glue aqueous solution is metatitanic acid powder quality
35%~45%；The additional amount of the pore creating material is the 3%~5% of metatitanic acid powder quality.
2. a kind of preparation method of TiO 2-based catalyst carrier according to claim 1, which is characterized in that described inclined
Metatitanic acid powder is prepared by the intermediate product metatitanic acid using Titanium White Production By Sulfuric Acid Process through drying, crushing, the metatitanic acid
The specific surface area of powder is 150m2/ g~200m2/g。
3. a kind of preparation method of TiO 2-based catalyst carrier according to claim 1, which is characterized in that described to make
Hole agent is carboxymethyl cellulose or hydroxypropyl cellulose.
4. a kind of preparation method of TiO 2-based catalyst carrier according to claim 1, which is characterized in that the oxygen
Changing aluminium hydrate is boehmite or aluminium hydroxide.
5. a kind of preparation method of TiO 2-based catalyst carrier according to claim 1, which is characterized in that the baking
Dry process are as follows: first in 60 DEG C~80 DEG C dry 2h~3h, then in 110 DEG C~120 DEG C dry 3h~5h.
6. a kind of preparation method of TiO 2-based catalyst carrier according to claim 1, which is characterized in that the roasting
The temperature of burning is 350 DEG C~500 DEG C, and the time is 2h~4h.
7. a kind of preparation method of TiO 2-based catalyst carrier according to claim 1, which is characterized in that described two
The specific surface area of titania-based catalyst carrier is 100m2/ g~160m2/ g, compression strength are 100N/cm~120N/cm.
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| CN114042445A (en) * | 2021-11-30 | 2022-02-15 | 西安向阳航天材料股份有限公司 | Titanium dioxide-based catalyst carrier and preparation method thereof |
| CN114433049A (en) * | 2022-02-11 | 2022-05-06 | 射洪科瑞沃环保技术有限公司 | Titanium oxide sulfur recovery catalyst with high specific surface area and preparation method thereof |
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